亚微米介孔二氧化硅微球的制备及其弹性模量的拟合计算
|
摘要
在室温条件下以十六烷基三甲基溴化铵为表面活性剂制备亚微米级介孔二氧化硅(mSiO_2)微球,通过小角XRD、FESEM、TEM和孔分布测试等手段对样品进行结构表征。结果表明:所得mSiO_2微球的粒径为(316±11)nm,样品内部存在蠕虫状放射状介孔孔道,其孔径多集中在2.5 nm。利用AFM力曲线测试技术对单个mSiO_2微球的弹性响应进行评价,通过解析所记录的力—位移曲线,分别结合Hertzain模型和Sneddon模型对样品的压缩弹性模量进行拟合计算。利用Hertzain弹性接触模型计算得出的弹性模量平均值为5.30 GPa,在Sneddon模型条件下获得的弹性模量平均值为16.50 GPa,与现有文献中关于介孔氧化硅薄膜材料弹性模量的报道值(3~16 GPa)基本相当。
The submicrometer mesoporous silica(mSiO_2) microspheres were synthesized using cetyltrimethylammonium bromide as surface active agent under room temperature. The structural characteristics of the obtained samples were characterized by low-angle X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy and nitrogen adsorption-desorption methods. The results show that the particle size of mSiO_2 microspheres with worm-like and radial channels is(316±11) nm, and the pore diameter of mesochannels is 2.5 nm. The elastic responses of mSiO_2 microspheres deposited on a rigid substrate were evaluated by using an atomic force microscope. The compressive elastic modulus of individual microsphere was fitted and calculated by analyzing the AFM force-displacement curves on the basis of the Hertzain and Sneddon contact models. The results show that the average elastic moduli are 5.30(Hertzain model) and 16.50 GPa(Sneddon model), which are comparable with the reported elastic moduli for mesoporous silica film materials(3-16 GPa).
The submicrometer mesoporous silica(mSiO_2) microspheres were synthesized using cetyltrimethylammonium bromide as surface active agent under room temperature. The structural characteristics of the obtained samples were characterized by low-angle X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy and nitrogen adsorption-desorption methods. The results show that the particle size of mSiO_2 microspheres with worm-like and radial channels is(316±11) nm, and the pore diameter of mesochannels is 2.5 nm. The elastic responses of mSiO_2 microspheres deposited on a rigid substrate were evaluated by using an atomic force microscope. The compressive elastic modulus of individual microsphere was fitted and calculated by analyzing the AFM force-displacement curves on the basis of the Hertzain and Sneddon contact models. The results show that the average elastic moduli are 5.30(Hertzain model) and 16.50 GPa(Sneddon model), which are comparable with the reported elastic moduli for mesoporous silica film materials(3-16 GPa).
引文
[1]赵清亮,孙智源,郭兵.碳化硅圆柱槽微结构表面的化学机械抛光[J].机械工程学报,2015,51(15):183-189.ZHAO Qing-ling,SUN Zhi-yuan,GUO Bing.Chemical mechanical polishing of micro-structures on SSi C[J].Journal of Mechanical Engineering,2015,51(15):183-189.
[2]WANG Yong-guang,CHENA Yao,QI Fei,XING Zhan-wen,LIU Wei-wei.A molecular-scale analytic model to evaluate material removal rate in chemical mechanical planarization considering the abrasive shape[J].Microelectronic Engineering,2015,134:54-59.
[3]MATOVU J B,ONG P,LEUNISSEN L H A,BABU S V.Use of multifunctional carboxylic acids and hydrogen peroxide to improve surface quality and minimize phosphine evolution during chemical mechanical polishing of indium phosphide surfaces[J].Industrial&Engineering Chemistry Research,2013,52(31):10664-10672.
[4]VAKARELSKI I U,BROWN S C,BASIM G B,RABINOVICH Y I,MOUDGILET B M.Tailoring silica nanotribology for CMP slurry optimization:Ca2+cation competition in C12TAB mediated lubrication[J].ACS Applied Materials&Interfaces,2010,2(4):1228-1235.
[5]LIM J,PARK J,PARK J.Effect of iron(Ⅲ)nitrate concentration on tungsten chemical mechanical planarization performance[J].Applied Surface Science,2013,282:512-517.
[6]PI?EIRO A,BLACK A,MEDINA J,DIEGUEZ E,PARRA V.The use of potassium peroxidisulphate and Oxone?;as oxidizers for the chemical mechanical polishing of silicon wafers[J].Wear,2013,303(1/2):446-450.
[7]林广川,郭丹,解国新,潘国顺.抛光液中离子浓度对化学机械抛光过程的影响[J].中国表面工程,2015,28(4):54-61.LIN Guang-chuan,GUO Dan,JIE Guo-xin,PAN Guo-shun.Influence of ionic concentration of slurry on process of chemical mechanical polishing[J].China Surface Engineering,2015,28(4):54-61.
[8]王建超,牛新环,李睿琦,赵欣.p H调节剂对蓝宝石衬底CMP的影响[J].半导体技术,2016,41(8):615-619.WANG Jian-chao,NIU Xin-huan,LI Rui-qi,ZHAO Xin.Influence of different p H regulators on the sapphire substrate CMP[J].Semiconductor Technology,2016,41(8):615-619.
[9]YAN Wei-xia,WANG Liang-yong,LIU Wei-li,SONG Zhi-tang.Role of the lysine as a complexing agent in Ge2Sb2Te5 chemical mechanical polishing slurries[J].Electrochimica Acta,2014,135:101-107.
[10]LEI Hong,TONG Kai-yu,WANG Zhan-yong.Preparation of Ce-doped colloidal Si O2 composite abrasives and their chemical mechanical polishing behavior on sapphire substrates[J].Materials Chemistry and Physics,2016,172:26-31.
[11]CHEN Yang,LI Ze-feng,QIN Jia-wei,CHEN Ai-lian.Monodispersed mesoporous silica(m Si O2)spheres as abrasives for improved chemical mechanical planarization performance[J].Journal of Materials Science,2016,51:5811-5822.
[12]CHEN Ai-lian,ZHANG Ze-fang,LI Xia-zhang,CHEN Yang.Evaluation of oxide chemical mechanical polishing performance of polystyrene coated ceria hybrid abrasives[J].Journal of Materials Science:Materials in Electronics,2016,27:2919-2925.
[13]ARMINI S,VAKARELAKI I U,WHELAN C M,MAEX K,HIGASHITANI K.Nanoscale indentation of polymer and composite polymer-silica core-shell submicrometer particles by atomic force microscopy[J].Langmuir,2007,23(4):2007-2014.
[14]陈杨,穆为彬,陆锦霞.核壳结构PS/Ce O2复合微球弹性模量的AFM测定[J].摩擦学学报,2012,32(1):1-7.CHEN Yang,MU Wei-bin,LU Jin-xia.Determination of elastic moduli of composite PS/Ce O2 core-shell microspheres by atomic force microscope[J].Tribology,2012,32(1):1-7.
[15]陈爱莲,钱程,苗乃明,陈杨.壳层厚度对核-壳结构PS-Si O2杂化颗粒压缩弹性模量的影响[J].复合材料学报,2015,32(4):1125-1131.CHEN Ai-lian,QIAN Cheng,MIAO Nai-ming,CHEN Yang.Effect of shell thickness on the compressive elastic moduli for core-shell PS-Si O2 hybrid particles[J].Acta Materiae Compositae Sinica,2015,32(4):1125-1131.
[16]陈爱莲,汪亚运,陈杨.设计与制备具有放射状介孔壳层的PS/MSi O2复合磨料及其抛光氧化硅片效果[J].中国有色金属学报,2016,26(2):392-401.CHEN Ai-lian,WANG Ya-yun,CHEN Yang.Design and fabrication of PS/MSi O2 composite abrasives with radial mesoporous shells and their polishing behavior for oxidized silicon wafer[J].The Chinese Journal of Nonferrous Metals,2016,26(2):392-401.
[17]WILLIFORD R E,ADDLEMAN R S,LI X S,ZEMANIAN T S,BIRNBAUM J C,FRYXELL G E.Pore shape evolution in mesoporous silica thin films:From circular to elliptical to rectangular[J].Journal of Non-Crystalline Solids,2005,351:2217-2223.
[18]JAUFFRèSA D,YACOU C,VERDIER M,DENDIEVEL R,AYRAL A.Mechanical properties of hierarchical porous silica thin films:Experimental characterization by nanoindentation and finite element modeling[J].Microporous and Mesoporous Materials,2011,140:120-129.
[19]ZHANG Kun,XU Lang-lang,JIANG Jin-gang,CALI N,LAM K F,ZHANG San-jun,WU Hai-hong,WU Guang-dong,ALBELA B,BONNEVIOT L,WU Peng.Facile large-scale synthesis of monodisperse mesoporous silica nanospheres with tunable pore structure[J].Journal of the American Chemical Society,2013,135(7):2427-2430.
[20]郝仕油,邓黄秀,章国栋.表面氨基高密度化介孔氧化硅的合成及其高效去除酸性橙7[J].无机化学学报,2016,32(2):232-240.HAO Shi-you,DENG Huang-xiu,ZHANG Guo-dong.Synthesis and efficient removal of acid orange of mesoporous silicas with high surface amino-loading[J].Chinese Journal of Inorganic Chemistry,2016,32(2):232-240.
[21]GUO Dan,LI Jing-nan,XIE Guo-xin,WANG Yuan-yuan,LUO Jian-bin.Elastic properties of polystyrene nanospheres evaluated with atomic force microscopy:Size effect and error analysis[J].Langmuir,2014,30:7206-7212.
[22]SMIRNOV W,KRIELE A,HOFFMANN R,SILLERO E,HEES J,WILLIAMS O A,YANG N,KRANZ C,NEBEL C E.Diamond-modified AFM probes:From diamond nanowires to atomic force microscopy-integrated boron-doped diamond electrodes[J].Analytical Chemistry,2011,83:4936-4941.
[23]WILLIFORD R E,LI X S,ADDLEMAN R S,FRYXELL G E,BASKARAN S,BIRNBAUM J C,COYLE C,ZEMANIAN T S,WANG C,COURTNEY A R.Mechanical stability of templated mesoporous silica thin films[J].Microporous and Mesoporous Materials,2005,85:260-266.
[24]CHEMIN N,KLOTZ M,ROUESSAC V,AYRAL A,BARTHEL E.Mechanical properties of mesoporous silica thin films:Effect of the surfactant removal processes[J].Thin Solid Films,2006,495:210-213.
[25]NIU Chao,WU Xiao-qing,REN Wei,CHEN Xiao-feng,SHI Peng.Mechanical properties of low k Si O2 thin films template by PVA[J].Ceramics International,2015,41:S365-S369.
[26]李娃,李凤云,史志胜,黄珏,蔡强,张伟.毫米级轻质高强度多孔二氧化硅球的制备与表征[J].高等学校化学学报,2015,36(9):1655-1660.LI Wa,LI Feng-yun,SHI Zhi-sheng,HUANG Jue,CAI Qiang,ZHANG Wei.Preparation and characterization of strong-lightweight porous silica spheres in millimeter scale[J].Chemical Journal of Chinese Universities,2015,36(9):1655-1660.
[27]ROMEIS S,PAUL J,HERRE P,de LIGNY D,SCHMIDT J,PEUKERT W.Local densification of a single micron sized silica sphere by uniaxial compression[J].Scripta Materialia,2015,108:84-87.
[28]ZHENG Hai-mei,Ying Shirley Meng,ZHU Yi-mei.Frontiers of in situ electron microscopy[J].MRS Bulletin,2015,40:12-18.
[2]WANG Yong-guang,CHENA Yao,QI Fei,XING Zhan-wen,LIU Wei-wei.A molecular-scale analytic model to evaluate material removal rate in chemical mechanical planarization considering the abrasive shape[J].Microelectronic Engineering,2015,134:54-59.
[3]MATOVU J B,ONG P,LEUNISSEN L H A,BABU S V.Use of multifunctional carboxylic acids and hydrogen peroxide to improve surface quality and minimize phosphine evolution during chemical mechanical polishing of indium phosphide surfaces[J].Industrial&Engineering Chemistry Research,2013,52(31):10664-10672.
[4]VAKARELSKI I U,BROWN S C,BASIM G B,RABINOVICH Y I,MOUDGILET B M.Tailoring silica nanotribology for CMP slurry optimization:Ca2+cation competition in C12TAB mediated lubrication[J].ACS Applied Materials&Interfaces,2010,2(4):1228-1235.
[5]LIM J,PARK J,PARK J.Effect of iron(Ⅲ)nitrate concentration on tungsten chemical mechanical planarization performance[J].Applied Surface Science,2013,282:512-517.
[6]PI?EIRO A,BLACK A,MEDINA J,DIEGUEZ E,PARRA V.The use of potassium peroxidisulphate and Oxone?;as oxidizers for the chemical mechanical polishing of silicon wafers[J].Wear,2013,303(1/2):446-450.
[7]林广川,郭丹,解国新,潘国顺.抛光液中离子浓度对化学机械抛光过程的影响[J].中国表面工程,2015,28(4):54-61.LIN Guang-chuan,GUO Dan,JIE Guo-xin,PAN Guo-shun.Influence of ionic concentration of slurry on process of chemical mechanical polishing[J].China Surface Engineering,2015,28(4):54-61.
[8]王建超,牛新环,李睿琦,赵欣.p H调节剂对蓝宝石衬底CMP的影响[J].半导体技术,2016,41(8):615-619.WANG Jian-chao,NIU Xin-huan,LI Rui-qi,ZHAO Xin.Influence of different p H regulators on the sapphire substrate CMP[J].Semiconductor Technology,2016,41(8):615-619.
[9]YAN Wei-xia,WANG Liang-yong,LIU Wei-li,SONG Zhi-tang.Role of the lysine as a complexing agent in Ge2Sb2Te5 chemical mechanical polishing slurries[J].Electrochimica Acta,2014,135:101-107.
[10]LEI Hong,TONG Kai-yu,WANG Zhan-yong.Preparation of Ce-doped colloidal Si O2 composite abrasives and their chemical mechanical polishing behavior on sapphire substrates[J].Materials Chemistry and Physics,2016,172:26-31.
[11]CHEN Yang,LI Ze-feng,QIN Jia-wei,CHEN Ai-lian.Monodispersed mesoporous silica(m Si O2)spheres as abrasives for improved chemical mechanical planarization performance[J].Journal of Materials Science,2016,51:5811-5822.
[12]CHEN Ai-lian,ZHANG Ze-fang,LI Xia-zhang,CHEN Yang.Evaluation of oxide chemical mechanical polishing performance of polystyrene coated ceria hybrid abrasives[J].Journal of Materials Science:Materials in Electronics,2016,27:2919-2925.
[13]ARMINI S,VAKARELAKI I U,WHELAN C M,MAEX K,HIGASHITANI K.Nanoscale indentation of polymer and composite polymer-silica core-shell submicrometer particles by atomic force microscopy[J].Langmuir,2007,23(4):2007-2014.
[14]陈杨,穆为彬,陆锦霞.核壳结构PS/Ce O2复合微球弹性模量的AFM测定[J].摩擦学学报,2012,32(1):1-7.CHEN Yang,MU Wei-bin,LU Jin-xia.Determination of elastic moduli of composite PS/Ce O2 core-shell microspheres by atomic force microscope[J].Tribology,2012,32(1):1-7.
[15]陈爱莲,钱程,苗乃明,陈杨.壳层厚度对核-壳结构PS-Si O2杂化颗粒压缩弹性模量的影响[J].复合材料学报,2015,32(4):1125-1131.CHEN Ai-lian,QIAN Cheng,MIAO Nai-ming,CHEN Yang.Effect of shell thickness on the compressive elastic moduli for core-shell PS-Si O2 hybrid particles[J].Acta Materiae Compositae Sinica,2015,32(4):1125-1131.
[16]陈爱莲,汪亚运,陈杨.设计与制备具有放射状介孔壳层的PS/MSi O2复合磨料及其抛光氧化硅片效果[J].中国有色金属学报,2016,26(2):392-401.CHEN Ai-lian,WANG Ya-yun,CHEN Yang.Design and fabrication of PS/MSi O2 composite abrasives with radial mesoporous shells and their polishing behavior for oxidized silicon wafer[J].The Chinese Journal of Nonferrous Metals,2016,26(2):392-401.
[17]WILLIFORD R E,ADDLEMAN R S,LI X S,ZEMANIAN T S,BIRNBAUM J C,FRYXELL G E.Pore shape evolution in mesoporous silica thin films:From circular to elliptical to rectangular[J].Journal of Non-Crystalline Solids,2005,351:2217-2223.
[18]JAUFFRèSA D,YACOU C,VERDIER M,DENDIEVEL R,AYRAL A.Mechanical properties of hierarchical porous silica thin films:Experimental characterization by nanoindentation and finite element modeling[J].Microporous and Mesoporous Materials,2011,140:120-129.
[19]ZHANG Kun,XU Lang-lang,JIANG Jin-gang,CALI N,LAM K F,ZHANG San-jun,WU Hai-hong,WU Guang-dong,ALBELA B,BONNEVIOT L,WU Peng.Facile large-scale synthesis of monodisperse mesoporous silica nanospheres with tunable pore structure[J].Journal of the American Chemical Society,2013,135(7):2427-2430.
[20]郝仕油,邓黄秀,章国栋.表面氨基高密度化介孔氧化硅的合成及其高效去除酸性橙7[J].无机化学学报,2016,32(2):232-240.HAO Shi-you,DENG Huang-xiu,ZHANG Guo-dong.Synthesis and efficient removal of acid orange of mesoporous silicas with high surface amino-loading[J].Chinese Journal of Inorganic Chemistry,2016,32(2):232-240.
[21]GUO Dan,LI Jing-nan,XIE Guo-xin,WANG Yuan-yuan,LUO Jian-bin.Elastic properties of polystyrene nanospheres evaluated with atomic force microscopy:Size effect and error analysis[J].Langmuir,2014,30:7206-7212.
[22]SMIRNOV W,KRIELE A,HOFFMANN R,SILLERO E,HEES J,WILLIAMS O A,YANG N,KRANZ C,NEBEL C E.Diamond-modified AFM probes:From diamond nanowires to atomic force microscopy-integrated boron-doped diamond electrodes[J].Analytical Chemistry,2011,83:4936-4941.
[23]WILLIFORD R E,LI X S,ADDLEMAN R S,FRYXELL G E,BASKARAN S,BIRNBAUM J C,COYLE C,ZEMANIAN T S,WANG C,COURTNEY A R.Mechanical stability of templated mesoporous silica thin films[J].Microporous and Mesoporous Materials,2005,85:260-266.
[24]CHEMIN N,KLOTZ M,ROUESSAC V,AYRAL A,BARTHEL E.Mechanical properties of mesoporous silica thin films:Effect of the surfactant removal processes[J].Thin Solid Films,2006,495:210-213.
[25]NIU Chao,WU Xiao-qing,REN Wei,CHEN Xiao-feng,SHI Peng.Mechanical properties of low k Si O2 thin films template by PVA[J].Ceramics International,2015,41:S365-S369.
[26]李娃,李凤云,史志胜,黄珏,蔡强,张伟.毫米级轻质高强度多孔二氧化硅球的制备与表征[J].高等学校化学学报,2015,36(9):1655-1660.LI Wa,LI Feng-yun,SHI Zhi-sheng,HUANG Jue,CAI Qiang,ZHANG Wei.Preparation and characterization of strong-lightweight porous silica spheres in millimeter scale[J].Chemical Journal of Chinese Universities,2015,36(9):1655-1660.
[27]ROMEIS S,PAUL J,HERRE P,de LIGNY D,SCHMIDT J,PEUKERT W.Local densification of a single micron sized silica sphere by uniaxial compression[J].Scripta Materialia,2015,108:84-87.
[28]ZHENG Hai-mei,Ying Shirley Meng,ZHU Yi-mei.Frontiers of in situ electron microscopy[J].MRS Bulletin,2015,40:12-18.